Time-Dependent Perturbation Theory

In summary, Time-Dependent Perturbation Theory is a mathematical technique used to study the behavior of quantum systems subject to varying external forces. It differs from Time-Independent Perturbation Theory in that it can handle time-varying perturbations and does not have a limitation on the size of the perturbation. Its applications include understanding atoms in intense laser fields and calculating transition rates. The main assumptions of this theory are a time-independent Hamiltonian, small perturbation, and a smooth switching of external forces. However, it may not be accurate for strong perturbations or in cases of degenerate energy levels or a large number of energy levels involved.
  • #1
PatsyTy
30
1
Note this isn't actually a homework problem, I am working through my textbook making sure I understand the derivation of certain equations and have become stuck on one part of a derivation.

1. Homework Statement


I am working through my text (Quantum Mechanics 2nd Edition by B.H Bransden & C.J Joachain) section 9.1 on Time-Dependant Perturbation Theory. Part way through their derivation they give the equation

[itex]i \hbar \sum_k \dot{c}_k (t)\psi_k^{(0)}e^{-\frac{iE_k^{(0)}t}{\hbar}}=\lambda \sum_kH'(t)c_k(t)\psi_k^{(0)}e^{-\frac{iE_k^{(0)}t}{\hbar}}[/itex]

where ##c_k## denotes the time-dependent coefficients, any factor with a ##(0)## superscript denotes a factor relating to the "unperturbed" state, ##\lambda## is just a constant (usually equal to one for physical systems) and ##H'## denotes the "perturbed" Hamiltonian.

From this equation the text states:

"Taking the scalar product with a function ##\psi_b^{(0)}## belonging to the set ##y_k^{(0)}## of unperturbed energy eigenfunctions, and using the fact that ##\langle \psi_b^{(0)} | \psi_a^{(0)} \rangle = \delta_{bk}##, we find that

[itex]\dot{c}_b (t) = i \hbar^{-1} \lambda \sum_k H'_{bk}(t)e^{i \omega_{bk} t} c_k(t)[/itex]

where ##H'_{bk}=\langle \psi_{b}^{(0)} | H' (t) | \psi_k^{(0)} \rangle## and ##\omega_{bk}=\frac{E_b^{(0)}-E_k^{(0)}}{\hbar}## is the Bohr angular frequency.

Homework Equations



Not sure if there are any not given really, it's mostly just rearranging everything

The Attempt at a Solution



So first I multiply both sides by ##e^{\frac{iE_k^{(0)}t}{\hbar}}## cancel it out on the L.H.S and bring all the big terms to the R.H.S giving

[itex]i \hbar \sum_k \dot{c}_k (t)\psi_k^{(0)}=\lambda \sum_k c_k(t)\psi_k^{(0)}e^{\frac{iE_k^{(0)}t}{\hbar}}H'(t)e^{-\frac{iE_k^{(0)}t}{\hbar}}[/itex]

I then change all the ##\psi_k^{(0)}## eigenfunctions to their ket representation

[itex]i \hbar \sum_k \dot{c}_k (t)| \psi_k^{(0)} \rangle=\lambda \sum_k c_k(t)e^{\frac{iE_k^{(0)}t}{\hbar}}H'(t)e^{-\frac{iE_k^{(0)}t}{\hbar}} | \psi_k^{(0)}\rangle[/itex]

I then multiply (i.e take the inner product) of the L.H.S and the R.H.S with ##\langle\psi_b^{(0)}|## giving

[itex]i \hbar \sum_k \dot{c}_k (t) \langle\psi_b^{(0)}| \psi_k^{(0)} \rangle=\lambda \sum_k c_k(t)\langle\psi_b^{(0)}|e^{\frac{iE_k^{(0)}t}{\hbar}}H'(t)e^{-\frac{iE_k^{(0)}t}{\hbar}} | \psi_k^{(0)}\rangle[/itex]

The portion of this equation that is giving me issues is how the ##k## subscript in ##\langle \psi_b^{(0)} | e^{\frac{iE_k^{(0)}t}{\hbar}}## changes to ##b## giving me ##\langle\psi_b^{(0)}|e^{\frac{iE_k^{(0)}t}{\hbar}}##. If I can get this I believe all the exponential terms are not operators so I can pull them out of the braket term to give me ##H'_{bk}=\langle \psi_{b}^{(0)} | H' (t) | \psi_k^{(0)} \rangle## and and then I can just combine the exponentials to give me the Bohr angular frequency term.

I'm sure I am doing something small (or something big) wrong somewhere but I just can't figure it out. Any help would be greatly appreciated!

Thanks!
 
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  • #2
PatsyTy said:
So first I multiply both sides by ##e^{\frac{iE_k^{(0)}t}{\hbar}}## cancel it out on the L.H.S and bring all the big terms to the R.H.S giving

[itex]i \hbar \sum_k \dot{c}_k (t)\psi_k^{(0)}=\lambda \sum_k c_k(t)\psi_k^{(0)}e^{\frac{iE_k^{(0)}t}{\hbar}}H'(t)e^{-\frac{iE_k^{(0)}t}{\hbar}}[/itex]
This is certainly one of the big wrong things - the exponential factor is part of the sum and is not a global factor, so you can't just multiply both sides by it.
 
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  • #3
Fightfish said:
This is certainly one of the big wrong things - the exponential factor is part of the sum and is not a global factor, so you can't just multiply both sides by it.

Thanks, I see that now. Guess I'll be taking a look at it tomorrow and see if I can think of another way.
 
  • #4
Start with what the text says and take the scalar product. Also, remember that ##H'(t)## is an operator, so you can't move ##\psi_k^{(0)}## past it like you did on the RHS.
 
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  • #5
vela said:
Start with what the text says and take the scalar product. Also, remember that ##H'(t)## is an operator, so you can't move ##\psi_k^{(0)}## past it like you did on the RHS.

Thanks for the reply! I managed to figure it out. I was getting confused thinking ##e^{-iE_k^{(0)}t/\hbar}## was also an operator. When I get home I'll write out what I did to make sure it's correct.

Thanks again!
 
  • #6
So I believe the solution is to just change the eigenfunctions to their ket representation and multiply through by ##\langle \psi_b^{(0)} |##

[itex]i \hbar \sum_k \dot{c}_k (t)\langle \psi_b^{(0)} | \psi_k^{(0)} \rangle e^{-\frac{iE_k^{(0)}t}{\hbar}}=\lambda \sum_kc_k(t)\langle \psi_b^{(0)} | H'(t)| \psi_k^{(0)} \rangle e^{-\frac{iE_k^{(0)}t}{\hbar}}[/itex]

Which reduces to

[itex]i \hbar \dot{c}_k (t) e^{-\frac{iE_b^{(0)}t}{\hbar}}=\lambda \sum_kc_k(t)H'_{ba} e^{-\frac{iE_k^{(0)}t}{\hbar}}[/itex]

then move the exponential over to the R.H.S and combine the terms for the Bohrn angular frequency to give what we want

[itex] \dot{c}_k (t) =(i\hbar)^{-1}\lambda \sum_kH'_{bk} e^{-i\omega_{ba}t}c_k(t)[/itex]
 

1. What is Time-Dependent Perturbation Theory?

Time-Dependent Perturbation Theory is a mathematical technique used to study the behavior of quantum systems that are subject to external forces or perturbations that vary with time. It allows us to calculate the evolution of the system over time and predict its properties and behavior.

2. How is Time-Dependent Perturbation Theory different from Time-Independent Perturbation Theory?

Time-Independent Perturbation Theory is used for systems with stationary external forces, while Time-Dependent Perturbation Theory is used for systems where the external forces vary with time. Time-Independent Perturbation Theory also assumes that the perturbation is small, while Time-Dependent Perturbation Theory does not have this limitation.

3. What are the applications of Time-Dependent Perturbation Theory?

Time-Dependent Perturbation Theory has many applications in quantum mechanics, such as understanding the behavior of atoms in intense laser fields, studying the effects of external electromagnetic fields on atoms and molecules, and calculating the rates of transitions between different energy levels in atoms and molecules.

4. What are the main assumptions of Time-Dependent Perturbation Theory?

The main assumptions of Time-Dependent Perturbation Theory are that the system can be described by a time-independent Hamiltonian and that the perturbation is small compared to the unperturbed system. It also assumes that the external forces are switched on and off smoothly, and that the system is initially in a well-defined state.

5. Are there any limitations to Time-Dependent Perturbation Theory?

Yes, there are some limitations to Time-Dependent Perturbation Theory. It is most accurate for weak perturbations and may not give accurate results for strong perturbations. It also assumes that the perturbation is smooth, which may not always be the case in real systems. Additionally, it may not work well for systems with degenerate energy levels or when there is a large number of energy levels involved.

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